Process for the production of polymer images

ABSTRACT

WHEREBY SAID MONOMER IS SELECTIVELY POLYMERIZED AT THE AREAS HAVING SAID LATENT IMAGE. The individual moieties are further defined in the specification and claims.   V. OXYQUINOLINE DERIVATIVE   IV. Beta -NAPHTHYLAMINE OR A DERIVATIVE THEREOF   III. Alpha -NAPHTHYLAMINE OR A DERIVATIVE THEREOF   II. Beta -NAPHTHOL OR A DERIVATIVE THEREOF   A process for the formation of a polymer image which comprises adding at least one monomer of the group consisting of a vinylidene monomer and a vinyl monomer to a photographic silver halide emulsion layer having a latent image in the presence of radiation and in the presence of at least one compound selected from those represented by the following formulas: I. Alpha -NAPHTHOL OR A DERIVATIVE THEREOF

United States Patent [191 Hayakawa et al.

[ Apr. 1, 1975 PROCESS FOR THE PRODUCTION OF POLYMER IMAGES [75]Inventors: Yoshihide l-layakawa; Masato Satomura, both of Asaka, Japan[73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Oct. 4, 1972 [21] Appl. No.: 295,079

Related U.S. Application Data [63] Continuation-in-part of Scr. No.848,085. Aug. 6.

1969, abandoned.

[30] Foreign Application Priority Data Aug. 20, 1968 Japan 43-59401 [52]U.S. Cl 96/51, 96/351, 96/48 R,

96/50 R, 96/115 P [51] Int. Cl G03c 1/70, G03c 1/68 [58] Field of Search96/35.], 27, 48 R, 50 R.

[56] References Cited UNITED STATES PATENTS 5/1959 Tupis... 96/351l/l962 Ostcr 96/29 6/l97l Pclz ct al. 96/29 OTHER PUBLICATIONS Mees. C.E. K.. The Theory of the Photographic Process." 1942. pages 343 & 356.

Pl'illltll') Exuminvr-Ronald H. Smith Almrney. Agent, or Fi|'n1-Sughrue,Rothwell, Mion, Zinn and Macpeak i. a-naphthol or a derivative thereofii. B-naphthol or a derivative thereof R7 on iii. a-naphthylamine or aderivative thereof iv. B-naphthylamine or a derivative thereof R R a NR2R6 3 v. oxyquinoline derivative whereby said monomer is selectivelypolymerized at the areas having said latent image. The individualmoieties are further defined in the specification and claims.

33 Claims, N0 Drawings PROCESS FOR THE PRODUCTION OF POLYMER IMAGESCROSS-REFERENCE TO RELATED APPLICATIONS The present application is aContinuation-In-Part Application of our earlier co-pending ApplicationSer. No. 848,085 filed Aug. 6, 1969, now abandoned, and claims priorityfrom Aug. 20, 1968, based on Japanese Patent Application Ser. No.59401/68.

BACKGROUND OF THE INVENTION 1. Field of the Invention The presentinvention relates to a process for the formation of polymer images andmore particularly to a process for selectively forming polymer images atthe areas corresponding to photographic latent imagebearing areas by theaction of a photographic silver halide emulsion and a reducing agent.

2. Description of the Prior Art There have been proposed variousprocesses of forming images by the formation of highly polymerizedcompounds by the photopolymerization of vinyl compounds. It has alsobeen proposed to directly cause photopolymerizations using silverhalides as catalysts (British Pat. No. 866,631; and S. Levinos et al.,Photographic Science and Engineering, Vol. 6, pages 222-226 (1962). Itis believed, in this reaction, that the photo-induced decompositionproduct of the silver halide serves as a polymerization catalyst, andthe sensitivity to light of this reaction does not reach the level whichis easily attained by ordinary development of silver halide particlesAlso, it has been proposed to form, imagewise, highly polymerizedcompounds by polymerizing vinyl compounds using as a catalyst a silverimage or unreacted silver halide after the development of an exposedsilver halide emulsion with an ordinary developing solution (BelgianPat. No. 642,477). This procedure has the disadvantage that thedevelopment and polymerization should be conducted separately. It istheoretically of great interest to effect the polymerization of vinylcompounds by the oxidation product, or intermediate thereof, formed inthe course of development of a photographic silver halide emulsion by areducing agent in the presence of the vinyl compounds, since it can beexpected that, in this procedure, the polymerization is effected by bothof amplifying effect of development and that of chain polymerization. Ithas already been proposed to effect such a reaction using as a reducingagent a benzenoid compound having at least two hydroxyl, amino oralkylor aryl-substituted amino groups in orthoor para-positions to eachother on a benzene ring (U.S. Pat. No. 3,019,104 and G. Oster; Nature;Vol. 180, page 1275 (1957)).

Moreover, other investigators have reported that they could not performthe experiments of these procedures with success (S. Levinos and F. W.H. Mueller; Photographic Science and Engineering, Vol. 6, page 222(1962).

SUMMARY OF THE INVENTION An object of the present invention is toconvert a latent image on a photographic silver halide emulsion layer,given by electromagnetic waves or particle rays, into an image of ahighly polymerized substance by a simple procedure.

Another object of this invention is to obtain a polymer image having thedesired properties by employing this procedure in recording or printing.

The inventors have discovered that the polymerization of a vinylcompound is effected by reducing a silver halide, in the presence of thevinyl compound, with a naphthol, a naphthylamine, an oxyquinoline orderivatives thereof as disclosed hereinafter. In cases where the silverhalide is in the form of a silver halide photographic emulsion, thereaction proceeds at a higher rate when the silver halide grains controldevelopment centers that when the grains have no development centers, sothat the polymerization can be selectively performed, with properselection of reaction conditions and reaction time, in the areas of theemulsion where the silver halide particles containing centers ofdevelopment exist; that is, in the case where the photographic emulsionlayer has a latent image.

DETAILED DESCRIPTION OF THE INVENTION The objects of the presentinvention are attained by employing the fact mentioned above; that is,by subjecting a silver halide photographic emulsion layer having aphotographic latent image to the action of a naphthol, a naphthylamine,or an oxyquinoline as described below in the presence of a polymerizablevinyl com pound to thererby selectively polymerize the vinyl compound inthe areas of the emulsion layer bearing the latent image.

The feature of the naphthol, naphthylamine, and oxyquinoline (or theirderivatives) used in the present invention is that when the compound hasmore than 2 amino groups of hydroxyl groups, the oxidized type thereofcan be shown by the following conjugate type as Kekules structure:

Example 1.

Example 2.

Example 3.

In particular, when the aforesaid compound has two amino groups and/orhydroxy groups in one ring thereof, the compound is a 1,2- or2,3-substituted one, which is also a feature of the compound.

Typical examples of the naphthols, naphthylamines, oxyquinolines, andderivatives thereof used in the present invention are as follows:

i. a -naphthol or derivative thereof:

wherein R represents a hydrogen atom, a sulfone group, a substitutedaryl group or a chlorine atom; R represents a hydrogen atom or asulfamoyl group; R represents a hydrogen atom, a sulfone group, or achlorine atom; R represents a hydrogen atom, a sulfone group, a hydroxylgroup, an amino group or an acylamino group; R represents a hydrogenatom, a car- ,boxyl group or a sulfone group; and R represents ahydrogen atom, a hydroxyl group or an amino group.

ii. B -naphthol or derivative thereof:

R OH

wherein R represents a hydrogen atom, a substitutedalkyl group, an aminogroup, or a hydroxyl group; R represents a hydrogen atom or a sulfonegroup; and R represents a hydrogen atom, an amino group or a hydroxylgroup.

iv. B -naphthylamine or derivative thereof:

wherein R represents a hydrogen atom or an amino group; R represents ahydrogen atom, a sulfone group or an amino group; R represents ahydrogen atom or I i a sulfone group; R represents a hydrogen atom or asulfone group; and R represents a hydrogen atom, a m

sulfone group or a hydroxyl group.

v. Oxyquinoline derivative:

wherein when R is a hydroxyl group, R represents a hydrogen atom or acarboxyl group and R. represents a hydrogen atom or a hydroxyl group andwhen 'R is i a hydroxyl group, R represents a carboxyl group and Rrepresents a hydrogen atom.

A photographic latent image is an invisible image formed in a silverhalide photographic emulsion by the I action of electromagnetic waves orparticle rays and can be converted into a visible image by development.

In the photographic emulsion layer utilized for forming a negativeimage, the latent image is formed by the formation of developmentcenters in silver halide grains irradiated by electromagnetic waves orparticle rays, while in a photographic emulsion layer utilized forforming a direct positive image, the latent image is formed by providingdevelopment centers in the whole silver halide grains present in thelayer and then removing the development centers by the irradiation ofelectromagnetic waves or particle rays (see, for. example, James and H.Huggins, Fundamentals of Photographic Theory, Chapters 3 and 4, 2ndedition, Morgam &,

Morgam Co.).

In the process of the present invention, the'aforesaid photographicsilver halide emulsion utilized for forming negative images as wellasthe photographic silver halide emulsion utilized for forming positiveimages i can be employed.

In the present invention, as a silver halide, photographic emulsion thatgives a negative image, an emulsion which is suitable for ordinarydeveloping out processes may conveniently be used. Thus, silverchloride,

silver bromide, silver chlorobromide, silver iodobro- I mide, and silverchloro-iodobromide photographic emulsions can be used. Chemicalsensitization and optical sensitization which are applicable to ordinaryphotographic emulsionscan be applied to the silverhalide emulsions forthe present invention. Thus, sulfur sensitization and noble metalsensitization are applicable for chemical sensitization (see, forexample, P. Glafkides,

Chimie Photographic, 2nd edition, Photocinema Paul Montel, Paris 1957pp. 247-301). As foroptical sensitization, optical sensitizers forordinary photographic emulsions, such as Cyanine dyes and mer cocyaninedyes, can be used conveniently (see, for example, Kikuchi et al., KagakuShashin Benran (Hand-' book of Scientific Photography), Vol. II, pp.15-241, Maruzen Co., 1959). The emulsion to be usedin the presentinvention may also contain stabilizers as employed in conventionalphotographic techniques.

The direct positive silver halide emulsion which can be employed in thepresent invention may be prepared by applying solarization, the Herscheleffect, the Clayden effect or the Sabatier effectfFull explanations of:

these effects are given in Chapter 6 and 7,C.E.K.

Mees, The Theory of the: Photographic Process; 2nd edition, published byMacMillan Co., 1954. To prepare direct positive silver halide emulsionsby solarization, a silver halide emulsion susceptible to solarization isprepared, and then subjected to uniform exposure of light or to theaction of a chemical to render it developable without image exposure.Methods of preparation of such emulsions are disclosed in, e.g., BritishPat. Nos. 443,245 and 462,730.

The Herschel effect is produced by exposing a photographic emulsionwhich has been rendered developable by a uniform exposure to light ofshorter wave length or a uniform action of a chemical reagent to a lightof longer wave length. In this case, it is preferable to use a silverhalide emulsion containing for the most part silver chloride and adesensitizer, such as pynakryptol yellow or phenosafranine, to enhancethe effect. A method of preparing the direct positive emulsions applyingthe Herschel effect is disclosed in, e.g., British Pat. No. 667,206 andU.S. Pat. No. 2,857,273.

In order to directly obtain a positive image by using the Claydeneffect, it is necessary to subject an emulsion overall exposure to lightof a relatively low intensity after imagewise exposure to light of ahigh intensity for a short period of time. The areas of the emulsionwhich have not been exposed to the irradiation of the high intensitylight become developable after this overall exposure.

The Sabatier effect-is produced by exposing to a uniform action of lightor a chemical reagent, in a state of immersion in a developing solution,a silver halide photographic emulsion layer that has received animagewise exposure to light to thereby give to a developability in thearea that has not been exposed to the imagewise exposure. The Claydeneffect and the Sabatier effect are easily and practically obtained insilver halide emulsions that have a tendency of yielding centers ofdevelopment, by the first exposure, in the inner portion, rather than inthe surface portion of the silver halide grains.

Methods of preparing emulsions having a tendency to yield internalcenters of development are disclosed in e.g., U.S. Pat. Nos. 2,592,250and 2,497,876, British Pat. No. 1,011,062 and German Pat. No. 1,207,791.

The photographic emulsions as mentioned above consist of dispersionsystems in which particles of silver halide are dispersed in a solutionof a high molecular weight polymer. Gelatin is widely employed as thehigh molecular weight polymer, while polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, carboxymethyl cellulose, oxyethyl ether anddextran may also be employed, alone or in mixtures with gelatin (see,e.g., F. Evva; Zeitschrift flir Wissenschafliche Photographie,Photophysik und Photochemie, Vol. 52, pp. 124, 1957). r i

Practical examples of the 'naphthols, naphthylamines, oxyquinolines, andderivatives thereof which may be employed in the present invention areas follows:

(l) -naphthol Continued 1o (2) Potassium l--na ahi:hol 2 -sulinnate SONa (3) Sodium .L-naphthol-4-sulfonate (4) Sodium l-naphthol-S-sulfonate)/5 naphthol (7) Z-naphthol-l-sodium sulfonic acid p Continued (30)l-amino-Znaphthol-4 sodium sulfonate (31) l-ami'no-S-naphthol (33)8-oxyquinoline (3 4) 4- 8-dihydroxyquinoline2 car aoxyl ic acidContinued OH (35) 4-hydroxyquinoline-2-cairboxylic acidt 3 7) 24-dichloro l-naphthol (38) 2 B-naphthalene-diamine Processes forpreparing the aforesaid compounds are well known in the art and theabove compounds are also commercially available.

In the present invention, silver halide is used as a form of the silverhalide photographic emulsion layer for increasing the difference inreactivity, that is, the selectivity in reaction betweenlthe areasirradiated by electromagnetic waves or particle rays andtthe areas notsubjected to such irradiation.

It has not yet been confirmed that the polymerization of this inventionisinitiated by a certain kind of inter mediate products formed by theco-action of the silver halide and the naphthol, naphthylamine orderivatives thereof as shown above but there are many reports about theoxidation of naphthols and these'reports also refer to theseintermediate products. For example, they are reported in T. J. Stone &W. A. Waters; Chem. & Ind., 213 (1964), M. Adams, M.S-. BloisJr, and R.

13 14 H. Sands; Chem. Phys, 28, 774 (1958), and R. Pum- In the reportmentioned above, the polymerization of mer and I. Veit; Chem. Ber., 86,412 (1953). Aca vinyl or vinylidene monomer usingthe intermediatecording to these reports, the formation of the following product formedby the oxidation was. not attempted. intermediate products are provided.Also, it is known that 1,2-dihydroxynaphthalene or OH i V QC 0 O- 0 9 II I Ila b IIc IId CH H 3 (iii) 0a CH CH CH3 7 III v Ivb The oxidation ofnaphthylamines is reported in, e.g., 1,5.-dihydroxynaphthalene iseffective as a developing L. Homer and J. Dehnert; Chem. Ber., 96, 786agent (C.E. K. Mees; The Theory of the Photographic (1963). According tothe teachings of the report, the 50 Process, Chapter 14', 2nd edition,published by Mcformation of the intermediate product is assumed to beMillan Co., 1954, New York). as follows: When each of the two rings ofnaphthalene has a hy- (v) NH 2 NH NH N I V VIa droxyl or an amino groupas in the present invention, it is considered that the polymerization ofthe vinyl or vinylidene compound is caused while the radical formed atdevelopment is notso stable. Furthermore, when one ring of thenaphthalene ring has two hydroxyl groups or amino groups at the1,4-positions, the radical formed at development is too stable toinitiate the polymerization, but when the groups are present at the 1,2-positions or 2,3-positions, the radical formed at development is not sostable and hence the polymerization of the vinyl or vinlidene compoundis caused. It is considered that the above phenomenon relates to thefact that in a so-called aromatic photographic developing agent having ahydroxyl group or an amino group, the activity of the developing agentof the p-substituent is generally higher than that of the o-substituteddeveloping agent, in other words, there are differences in stabilitiesof radicals between the two cases.

The reaction mechanism of the polymerization of a vinyl compound of avinylidene compound as the result of the reduction of silver halide bythe naphthol, naphthylamine, oxyquinoline or derivatives thereof,according to the present invention has not yet been determined. However,it is generally considered that, since a compound susceptible to radicalpolymerization is being used, and since it is being reacted in anaqueous media and also because a radical polymerization inhibitorretardsthe reaction, the polymerization proceeds through a radicalpolymerization mechanism. It has not yet been determined whether theradical is directly formed by the reaction of the reducing agent of thepresent invention with the silver halide, or whether the radicalis'formed by the co-action of the water, oxygen, etc. present in thesystem. However, although the influence of oxygen is not clear from .theabove-mentioned report, it is considered, when a naphthol for example isemployed as the reducing agent, that the following reaction will occur:

Furthermore, in the radicals thus formed according to the abovereaction, the following resonance structures are thought to exist, oneor more of which are considered to contribute to the initiation ofpolymerization.

Also, it is clear that the polymerization of. the vinyl compound orvinylidene compound occurs at the same time that the silverhalideisreduced, sincewhen the vinyl compound or the vinlidene compound isaddedto f V the reaction system after the reduction with thereducing agent,no polymerization is observed. Therefore, it M is considered that theintermediate product of the silver halide and the reducing agent used inthe present.in-. vention contributes to the initiation of the reaction.Also, when the reaction is stopped after a proper period of time, theirradiated portions are selectively ac- V companied with the formationof a highly polymerized. material, but when the reaction is furthercontinued,

the highly polymerized material is formed on the portions which have notbeen subjected to the irradiation.

This fact is thought to occur by the difference in the rate of theformation of (LC) caused by the difference between the reactivity of theirradiated silver halide and the non-irradiated silver halide. However,the fact A that the density of the unexposed portions reaches that ofthe exposed portions when the reaction is continued r for a longerperiod of time is the same as the phenomenon that occurs when thedevelopment is continued for a longer period of time in a conventionalphotographic process; that is, the entire portion, including theexposed. portions and non-exposed portions, are blackened. Thus,the factthat the aforesaid phenomenon ocr curs in the process of this inventionwill not injure the practicability of the present, invention.

ized compounds having various properties can beobtained in accordancewith vinyl compounds or vinylidene compounds to be used and, therefore,images hav-y ing quite excellent properties (such as dyeing property andchemical resistance which have never beenattained in the case ofemploying the cross-linkedprodnot of gelatin) can be obtained.

Furthermore, the present inventors have discovered thatif sulfite ionsare present in the reaction system of this invention, the polymerizationof the vinyl compounds or vinylidene compounds can be accelerated.Sulfite ions may be added to the reaction system, ei-

ther in the form of a compound which has sulfite ions originally presentin the molecule, suchas alkali metal sulfites or ammonium sulfite; or inthe form of a compound which will give sulfite ions as the result ofhydro-,

lysis in an aqueous solution, such as pyrosulfites of al kali metals orammonium or the adducts of bisulfites. with aldehyde such asformaldehyde or glyoxal. Al though the appropriate amount of sulfiteions to be added to the system-depends on the kind and amount of thereducing agent and the vinyl compound, the pH of the system, and thelike, more than 0.04, particularly more than 0.2, mole per liter of thereaction system is effective.

It is commonly known in the art to add a sulfite to photographicdeveloping solutions. But, in such cases, it is believed that thesulfite prevents both the autooxidation of the developing agent and theuneven occurrence of development by reacting with the oxidation productsof the developing agents such as hydroquinone or p-aminophenol (cf., forexample, C. E. K. Mees; Theory of the Photographic Process, 2nd edition,page 652 published by McMillan Co., 1954). It should be noted that sincethe intermediate product of the oxidation of the naphthol, thenaphthylamine, the oxyquinoline, or their derivatives initiates thepolymerization of the vinyl or vinylidene compound in the process ofthis invention, the polymerization-promoting effect of the sulfite ionsis essentially different from the action of removing the oxidationproducts, as in the orinary developing solutions mentioned above.

If the sulfite simply removes the oxidation products as in conventionaldeveloping processes, the polymerization would be inhibited rather thanpromoted.

While the mechanism of the action of sulflte ions in the process of thepresent invention is not yet clear, it is considered to be appropriatethat the sulfite ions prevent the polymerization inhibiting action ofoxygen. Also, the development and polymerization of the presentinvention can be promoted by using, together with the reducing agent, aconventional photographic developing agent or a quaternary salt. This isthe same phenomenon as in the case when a resorcinol, a phenol or aS-pyrazolone is used as the reducing agent, and a small amount of aconventional developing agent is added thereto, thus promoting thedevelopment and polymerization.

As conventional developing agents, there are the compounds representedby the formula A C=C B, wherein A and B each represents OH, -NH or -NHR,a so-called phenidone, i.e., l-aryl-3- oxopyrazolidine or a derivativethereof, and l-aryl-3- iminopyrazolidine. As mentioned before, theaforesaid developing agent by itself does not promote the polymerizationby development, but it is considered that it promotes the developingaction of a reducing agent having a polymerization initiating power, andthen promotes the polymerization of the monomers. As the quaternarysalt, there may be used a quaternary salt of pyridine such aslaurylpyridinium chloride. The fact that the use of the quaternary saltpromotes the development and polymerization is based on the fact that anordinary photographic silver halide emulsion contains halogen in anexcessive state, and that the surface of the silver halide particles inthe emulsion is negatively charged but the quaternary salt acts toneutralize the charges, thereby facilitating the approach of reducingagent and promoting the reaction.

As the vinyl compound in this invention, there is used an additionpolymerizable vinyl compound which is liquid or solid at normaltemperature, or a mixture of such vinyl monomers. Examples of such vinylcompounds are acrylamide, acrylonitrile, N-hydroxymethyl acrylamide,N-t-butylacrylamide, methacrylic acid, acrylic acid, calcium acrylate,sodium acrylate, methyl methacrylate, ethyl acrylate, vinylpyrrolidone,dicyclopentadiene methacrylate, vinyl butyrate, 2vinylpyridine,4-vinylpyridine, Z-methyl-N-vinylimidazole, potassium vinylbenzenesulfonate, and vinylcarbazole. In the process of this invention, a vinylcompound having more than 2 vinyl groups is particularly preferable andsuch a compound may be used alone or together with the 18 aforesaidvinyl compound having only one vinyl group. Examples of such a vinylcompound having more than two vinyl groups areN,N'-methylenebis-acrylamide, ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate, triethylene glycol dimethacrylate, polyethyleneglycol dimethyacrylate, divinylbenzene, bisphenol A dimethacrylate,butylene dimethacrylate, trimethylolpropane trimethacrylate,pentaerythritol tetraacrylate, and the like.

In the present invention, a water-soluble vinyl compound is convenientlyused but a water-insoluble vinyl compound may also be employed by addingit to the reaction system as an emulsion thereof. The emulsification maybe conducted by means of a suitable stirrer in the presence of asurface-active agent and/or a high molecular weight compound accordingto conventional methods.

Any electromagnetic wave or particle rays to which ordinary photographiclight-sensitive emulsions are sensitive can be utilized in the processof this invention. For example, the following may be utilized: visiblerays, ultraviolet rays, infrared rays having wave lengths shorter than1.3 microns, X-rays, gamma rays, alpha rays and electron rays.

For carrying out the process of this invention, it is necessary toconduct the two steps of irradiation by electromagnetic waves orparticle rays and of reduction and polymerization. Particularly, in therecording of images, it is necessary that the silver halide particles inthe emulsion change their locations little during the period between theirradiation by electromagnetic waves or particle rays and thepolymerization in the reaction system and, thus, it is preferable thatthe reaction system be maintained in a highly viscous liquid state or ina gel state. While photographic emulsions have some viscosity or can begelled since they contain natural or synthetic high molecular weightmaterials, a high molecular weight material may further be added to theemulsion if this property is insufficient.

During the irradiation by electromagnetic rays 'or particle rays, thesilver halide particles may be dispersed in an aqueous solution or heldin a dry gel. Thus, a highly viscous or gelled photographic emulsion maybe subjected to the irradiation on a support in an undried state or theemulsion may be subjected to the irradiation on a support in a driedstate. As the reduction and polymerization take place at the same time,the reduction must be conducted in the presence of a vinyl compound.While the compound of the present invention and the vinyl compound maybe incorporated-in 5 the photographic emulsion before exposure, one of;

them may be first incorporated in the emulsion before to the systemafterirradiation.

As the reduction and polymerization of this invention must be conductedin the presence of water, it is necessary to conduct the reaction in anaqueous solution or in a wet gel state.

The reaction of this invention proceeds smoothly in an alkaline stateand the most suitable pH of the reaction system depends on the kinds andconcentrations of silver halide, the reducing agent, and the highlypolymerized compound used as the medium and also on the reactiontemperature. The reaction can be performed at a pH greater than 6 but apH greater than 7 is particularly preferable.

When the photographic silver halide emulsion is used as a coatedemulsion layer on a support, the reaction may be performed by immersingthe photographic emulsion layer formed on a support in an alkalineaqueous solution, after the emulsion layer has been exposed to theelectromagnetic waves or particle rays. In this case, it is convenientto incorporate in the alkaline aqueous solution the reducing agent orthe vinyl compound.

Although the reactions can be readily stopped by reducing the pH of thereaction system to, e.g., less than 5, it may be stopped by cooling,removing the reactants by washing, dissolving the silver halide by aphotographic fixing solution, or adding a polymerization inhibitor tothe system.

When the high molecular weight compound (i.e., the vehicle for thesilver halide) and the vinyl monomer are formed into a layer, it ispreferable to add a small amount of a thermal polymerization inhibitorin order to prevent the spontaneous overall thermal polymerization ofthe vinyl monomer. As such a thermal polymerization inhibitor, any ofthe known thermal polymerization inhibitors utilized for radicalpolymerization may be utilized, such as: p-methoxyphenol, hydroquinone,an alkylhydroquinone, 2,6-di-t-butyl-p-cresol, and the like.

When the vinyl monomer is incorporated in the system from the first, theweight thereof is usually from 1.30 to 30 times, preferably one fourthto 4 times, the weight of the high molecular weight compound which isoriginally present in the system. The silver halide is conveniently usedin an amount by weight of from 1.20 to 2 times, preferably one tenth toone half times, the amount of the high molecular weight compoundoriginally present in the system. Also, when the reducing agent isincorporated in the system from the first, the amount of the reducingagent is preferably from one one-thousandth to 20 moles per mole of thesilver halide. Furthermore, when the aforesaid thermal polymerizationinhibitor is added to the system, the amount is conveniently from oneone-hundred thousandths to two one-hundredths of the weight of the vinylmonomer. When the vinyl monomer is incorporated in the processingsolution, it is preferable to dissolve it in as high a concentration aspossible, and hence the amount of the vinyl monomer is determined mainlyby its solubility in the processing solution. In the case where thenaphthol, the naphthylamine or the oxyquinoline, used as a reducingagent, is incorporated in the processing solution, the concentrationthereof is from one twothousandths to 5 moles, preferably from oneonehundreth to 1 mole per liter. 4

As in ordinary silver halide photographic processes, there can be anyinterval of time between the exposure to electromagnetic waves orparticle rays and the polymerization step. Depending on the propertiesof the photographic emulsion, the state where the system is allowed tostand, the length of the interval of time, the irradiation effect may bediminished to some extent and in such a case, the desired effect can beobtained by increasing the amount of exposure.

When the process of this invention is utilized for the recording ofimages, it is possible to utilize the various differences in solubility,light scattering, tackiness, dyereceptivity, and other physical andchemical properties between the vinyl monomer and the polymer thereof.By utilizing the difference in solubility, a relief image of a highmolecular weight material can be formed by dissolving off theunpolymerized portions after irradiaa tion and polymerization to leavethe highfmolecular" I weight material only at the irradiated portions.

In this case, it isconvenient that the high molecular! weight compoundoriginally present in the reaction sys-' tem be dissolved off togetherwith the unreacted mono- Q mer. Therefore, it is preferable that thehigh molecular weight compound originally present in the system be aso-called two-dimensional, linear and substantially uncrosslinked one,or a crosslinked one in which the main chain or the cross linkage may bereadily broken and that the high molecular weight compound be formed bythe polymerization of the monomer by the reaction be a so-calledthree-dimensional crosslinked one. For these purposes, it isconvenientto employ a compound having a plurality of vinyl groups as mentionedabove,; either alone or in combination with a compound having only onevinyl group. However, it is not essential to employ the compound havinga plurality of vinyl groups I since, even if the high molecular weightcompound thus formed is a two-dimensional Water-soluble one, there.

frequently occurs a remarkable difference in solubility between theareas where the high molecular weight compound is formed by the reactionand the areas where such a compound is not formed as the result of theco-action with the high molecular weight compound originally present inthe system (for example,

the case of polyacrylic acid and gelatin).

The images of the high molecular weight compound formed by the processof this invention can be utilized in various printing processes. i i

Furthermore, the process of this invention can be uti-- lized for theformation of color images. In such a case,

useful as the vinyl compound is a vinyl monomer having a group capableof having charges by electrolytic dissociation or by the addition of ahydrogen cation, to thereby form a polymer capable of having charges. byelectrolytic dissociation or by the addition of a hydrogen cation. Thepolymer images are then selectively dyed by a dye having the oppositecharge to that of the polymer. Also, the dye images thus formed maybetransferred to other supports by various methods.

Examples of such addition polymerizable vinyl compounds, capable ofhaving charges by electrolytic disso;

ciation or by the addition of a hydrogen cation used in the presentinvention are as follows: as a vinyl compound capable of providingnegative charges to the high molecular weight compound formed, thefollowing may be used: a vinyl compound having a carboxyl group, such asacrylic acid, methacrylic acid, itaconic I acid, and maleic acid;'avinyl compound having a metal salt or an ammonium salt of a carboxylicacid,,such as ammonium acrylate, sodium acrylate, potassium acrylate,calcium acrylate, magnesium acrylate, zinc acry-. late, cadmiumacrylate, sodium methacrylate,,calcium methacrylate, magnesiummethacrylate, zinc metha ble of providing positive charges to the highmolecular weight compound formed therefrom, the following may beutilized: a vinyl compound having a basic nitrogen atom, such as2-vinylpyridine, 4-vinylpyridine, 5-vinyl- Z-methylpyridine,N,N-dimethylaminoethyl acrylate,

N,N-dimethylaminoethyl methacrylate, N,N- diethylaminoethyl acrylate,and N,N-diethylaminoethyl methacrylate; and a vinyl compound having aquaternary nitrogen salt prepared from a base of the aforesaid vinylcompound having a basic nitrogen atom and methyl chloride, ethylbromide, dimethyl sulfate, diethyl sulfate, methyl p-toluenesulfonate,or the like. These compounds may be prepared by well known methods ormay be commercially available. These compounds may be used alone or incombination. Also, they may be used together with a water-solubleaddition polymerizable vinyl compound having no charge. As the lattertype of vinyl compound, there may be illustrated: acrylamide,N-hydroxymethyl acrylamide, methacrylamide, methyl methacrylate,vinylpyrrolidone, N,N-methylene-bis-acrylamide, triethylene glycoldimethacrylate, polyethylene glycol dimethacrylate, and the like. In thecase of using the vinyl compound having no charge, the reactivity andthe proportion of the vinyl compound must be so selected that a highmolecular weight compound having substantially no electrolyticallydissociating group is formed as the result of the polymerization of onlythe vinyl compound having no charge.

As a dye capable of having charges by electrolytic dissociation used inthe present invention, any conventional acid or basic dye may beemployed. Thus, when a vinyl compound capable of providing a highmolecular weight compound having negative charges is used, a basic dyeis used; whereas when a vinyl compound capable of providing a highmolecular weight compound having positive charges is employed, an aciddye is used. In other words, since a basic dye has positive charges, itselectively dyes a high molecular weight compound having negativecharges, whereas since an acid dye has negative charges, it selectivelydyes a high molecular weight compound having positive charges. Thus, adye image or a color image can be obtained in conformity with the highmolecular weight compound formed imagewise.

When gelatin is employed as the binder for the photographic emulsions,the isoelectric point of the gelatin must be considered for dyeingpurposes, since gelatin is an amphoteric electrolyte. That is, if the pHof the system is higher than the isoelectric point of gelatin, thegelatin has negative charges, while if the pH is lower, the gelatin haspositive charges. Accordingly, when a high molecular weight compoundhaving negative charges is formed, only the image of the high molecularweight compound can be dyed without dyeing the gelatin by dyeing theimagebearing emulsion layer with a basic dye. Also, when an emulsionlayer having the polymer image is first uniformly dyed at a pH higherthan the isoelectric point of gelatin, and, thereafter, the thus-dyedlayer is washed with a washing solution at a pH lower than theisoelectric point, only the dye on the areas of the emulsion layerhaving no polymer image is washed away, and hence only the areas havingthe polymer image can be kept in the dyed state.

When it is desired to dye the image of a high molecular weight compoundhaving positive charges with an acid dye, the image may be dyed at a pHhigher than the isoelectric point of the gelatin. Of course, if the pHof the reaction system is too high or too low, the solubility of the dyeis lowered and the electrolytic dissociation of the high molecularweight compound .to be charged is hindered. Thus, although the optimumpH range of the system depends on thekinds of vinyl compound and dyeemployed, as well as the kind of binder, such as gelatin, when normalgelatin is subjected to a lime processing and has an isoelectric pointof about 4.9, the pH is suitably 2.5-4.5 when a high molecular weightcompound having negative charges is dyed by a basic dye, and 5.0-8.0when a high molecular weight compound having positive charges is dyedwith an acid dye.

Typical examples of the acid dyes used in the process of this inventionare C.I. Acid Yellow 7 (Cl. 56,205), C.I. Acid Yellow 23 (C1. 19,140),C.I. Acid Red 1 (Cl. 18,050), C.I. Acid Red 52 (45,100), C.I. Acid Blue9 (CI. 42,090), C.l. Acid Blue 45, Cl. Acid Blue 62 (CI. 62,045), C.l.Acid Violet 7 (CI. 18,055), and the like. Also, typical examples of thebasic dyes used in the present invention are C.l. Basic Yellow 1 (Cl.49,005), C.I. Basic Yellow 2 (CI. 41,000), C.I. Basic Red 1 (C.l.45,160), C.I. Basic Red 2 (C.I. 50,240), C.I. Basic Blue 25 (Cl.52,025), C.l. Basic Violet 3 (Cl. 42,555), C.1. Basic Violet 10 (Cl.45,170), and the like. i

The numbers of the dyes given above are taken from Color Index (2ndedition).

For carrying out the process of this invention, it is necessary to firstconduct the reduction and polymerization after conducting theirradiation of the electromagnetic waves or particle rays, and thenconduct the dyeing.

By washing away only the unreacted vinyl monomer after the irradiationand the reduction and polymerization, polymer images can be obtained. Apolymer is generally less soluble in water than a monomer and hence whena high molecular weight compound originally present in a photographicsilver halide emulsion and used as a binder is left therein withoutbeing dissolved in water as gelatin, only the polymerized portion isleft to form an image since the polymer can scarcely diffuse intothegelatin phase. When a monomer having more than two vinyl groups isused together with the aforesaid vinyl monomer, the insolubility and thenondiffusion properties of the polymer can be further increased.

By dyeing the polymer images with the dye as mentioned above, the dyeimages or color images corresponding to the polymer images can beobtained. The dye images thus produced can be utilized as clear colorimages by removing the silver halide by a fixing procedure and furtherdissolving away the silver images by the action of an oxidizing agentand a solvent for the silver salt. When a reducing agent having a quitehigh polymerization initiating effect is employed, the polymerizationreaction occurs sufficiently even when only a very slight amount ofreduced silver is formed; and hence, in such a case, it is scarcely ornot at all necessary to remove the silver images by oxidation.

Furthermore, the dye images formed may be transferred to anothersupport. For carrying out the transfer, the emulsion layer having thedye images thereon is wetted with a solvent for the dye, such asmethanol, water, an aqueous solution of an acid, a base or a salt andthen the layer is brought into intimate contact with the surface of thesupport receiving the dye image. As such supports, there may be usedordinary paper, a paper having coated thereon a hydrophilic polymerlayer or a gelatin layer, and a film having coated thereon a hydrophilicpolymer layer or a gelatin layer.

When the dye images are transferred to a support having coated thereon agelatin layer, it is convenient to use a support treated with a mordantsuch as an aluminum salt, as is used in a conventional dye-transferprocess. When an image of a high molecular weight compound capable ofhaving charges is once formed, it is possible to make a number of copiestherefrom by dyeing and transferring as mentioned above. Also, sinceseveral copies of transferred images can be'obtained from only one dyeimage, and since one polymer image can be repeatedly dyed, many copiescan be easily obtained in accordance with the present invention.

The present invention will be further illustrated by the followingnon-limiting examples.

EXAMPLE 1 A photographic fine grain silver chlorobromide emulsioncontaining about 60 g./liter of gelatin and about 42 g./liter (assilver) of silver chlorobromide, and having a chlorine to bromine moleratio of 7:3, a pH of 5.8 and a pAg of.7.6 was divided into two parts,one of which was exposed to a fluorescent lamp. For carrying out theexposure, about 200 ml. of the emulsion, melted at about 35C., wasspread over a vat of 20 cm. X 25 cm. and then the liquid layer thusspread was exposed, with stirring, to a fluorescent lamp of about 300luxes for about minutes. Into a test tube of 1.6 cm. in diameter wascharged 2 ml. each of the exposed and the unexposed emulsion and, afteradding 6 ml. of water to each tube, 4.0 g. of acrylamide was dissolvedin each solution and then mole of sodium l-naphthol-4-sulfonate(compound 3) was added thereto. After stirring sufficiently, thetemperature of the system was adjusted to 60C. and the test tubes wereplaced in a heat insulating material. The insulating material wascovered by foamed polystyrene of about 2cm. in thickness and the wholesystem was immersed in a water bath kept at 60C. Thereafter, 4.0 ml. ofa l N aqueous sodium hydroxide solution was immediately added to eachsystem and the change of temperature was recorded by using athermister-type temperature recorder. The temperature of the exposedemulsion was increased by the heat of polymerization caused by thepolymerization of the acrylamide and, after about 1 18 minutes from thestart of the reaction, the temperature reached 915C. Further, thecontents of the test tube increased in viscosity because of thepolyacrylamide thus formed and were not dissolved even by a large amountof methanol.

On the other hand, the temperature of the unexposed emulsion systemreached only 75C.

Thus, it was clear from the generation of heat of poly- I merization andthe change in fluidity of the whole system that the polymerizationoccured in the exposed emulsion system. In fact, the reduction of thesilver halide might possibly generate heat in addition to that generatedby the polymerization reaction, butthe amount of heat generated by thereduction of the silver halide would be too slight to be detected as atemperature change in this system. For example, when hydroquinone wasused in the aforesaid procedure instead of sodiuml-naphthol-4-sulfonate, the silver halide was reduced into black silverbut no generation of heat was observed. Also, when sodiumZ-naphthol-l-sulfonate (compound 7) was used instead of sodiuml-naphthol- 4-sulfonate, the temperature of the exposed emulsion reached94C. after 123 minutes, whereas the temperature of the unexposedemulsion system reached only 80C.

From the aforesaid facts, that in the exposed emulsion system, thepolymerization preferentially occurred under the same conditions ascompared with the system 1 using the unexposed emulsion, it wasconfirmed that. the exposed emulsion took part in the reaction and, in

fact, caused the reaction.

EXAMPLE 2 photographic film was prepared as follows: Both surfaces of apolyethylene terephthalate film were undercoated, onto one of thesurfaces was then coated an an-- ti-halation layer and onto the otherwas coateda geIa-J tino fine particle silver halide emulsion containing100 g. of gelatin and about 0.7 mole of chlorine, about 0.3

mole of bromine and about 0.001 mole of iodine per 1 mole of silver, andhaving incorporated therein a merocyanine dye having the maximumsensitivity at 550m.

as a sensitizing dye, about 1.5 g. of mucochloric acid 1 I l per 100 g.of gelatin as a hardening agent, and a proper stabilizer and surfaceactive agent so that the layer thus coated contained 50 mg. of silverper 100 cm. of the layer. Then, a protective layer of gelatin havingathickness of about 0.8 micron was applied to the emulsion layer. Such aphotographic film is usually used forpreparing net images or line imagesby a photoengraving,

process.

A negave having line images was placed on the photographiclight-sensitive film, the system was exposed for 2 seconds to light ofabout 100 luxes, and then'the emulsion layer was immersed, under astable red light,

in a solution having the following composition:

Acrylamide g. Methylene-bis-acrylamide 10 g. l,7-dihydroxy-6-naphthoicacid 0.3 g. (compound 21) Potassium metabisulfite 3.0 g.

, Water ml.

2N NaOH solution the amount necessary to adjust the pH .to 11.5.

When the film was allowed to stand for 30 minutes at 30C., a slightimage was observed at the exposed arg t eas. When the reaction wasstopped by a '1 percent aqueous solution of acetic acid and, afterwashing the I layer with water, the gelatin of the emulsion layer wasdecomposed by using an aqueous solution of 1 percent gelatin-decomposingenzyme (trade name Bioprase PN 4); the gelatin at the unexposed areaswas completely washed away and undecomposed film was left at theunexposed areas, which showed that the polymerization selectivelyoccurredat the exposed areas. The same results were obtained when thesame procedure was conducted using 0.07 g. of S-aminQ-l-naphthol(compound 32) instead of. l,7-dihydroxy-6-naphthoic acid.

' EXAMPLE 3 The photographic light-sensitive film asin Example 2 wasexposed as in that example and processed. ina solution having thefollowing composition, to conduct the development and polymerization:

1-vinyl-2,3-dimethylimidazolium- 75 g. p-toluene sulfonate1,2-diaminonaphtha1ene (compound 27) 10 mg. Potassium rnetabisulfite 2amount necessary to adjust the pH to 11.6 75 ml.

2N solution of sodium hydroxide Water Thel-vinyl-2,3-dimethylimidazolium-p-toluene sulfonate had been prepared byreaction l-vinyl-2- methylimidazole and methyl p-toluene sulfonate at a10 normal temperature and recyrstallizing the product from ethanol andether. The melting point of the crystal Anhydrous sodium thiosulfate 150g. Potassium metabisulfite 15 g. Water to make 1 liter.

After sufficiently fixing and washing, the image thus formed was dyed bya 0.1 percent aqueous solution of a blue acid dye, Suminol Leveling SkyBlue R-extra conc., C.l. Acid Blue 62 and then washed for minutes with a1 percent aqueous solution of sodium bicarbonate to provide a blueimage.

As the brown image was a silver image, it could be readily dissolvedaway by a Farmers reducer. When dissolving away the silver image, aclear blue image could be obtained. Moreover, when the dyeing procedurewas conducted after the removal of the silver image, that is, when thesilver image was first removed to provide a colorless and transparentimage and then the image was dyed as above, a similar blue image couldbe obtained.

The color image thus formed could be transferred onto a paper. That is,when an ordinary writing paper was slightly wetted with methanol, andthe color image thus obtained was closely brought into contact with thepaper wetted, after 30 seconds the former was separated from the latter,and the color image was transferred onto the paper.

Also, when a gelatin layer of about microns was applied on the surfaceof a baryta-coated paper and the paper was immersed in an aqueoussolution of an alum followed by drying to provide a transfer paper, andthen the paper was after being wetted with water,

4O 2N-Sodium hydroxide brought into close contact with the color imagementioned above, and after 1 minute, the transfer paper was separatedfrom the latter, a clear blue image having a high density was obtainedon the transfer paper.

Furthermore, when the polymer image was immersed for 5 minutes in anaqueous solution of 0.1 percent of a red acid dye, Solar Rhodamine Bextra C.l. Acid Red 52 instead of immersing the aforesaid aqueoussolution of Suminol Leveling Sky Blue R extra cone. and then washed withwater, a sample was obtained where only the image portions were dyed inred.

The red image could also be transferred onto a writing paper wetted byethanol. Moreover, the color image could be transferred onto theaforesaid gelatin layer-containing transfer paper wetted by water.

Also, when the polymer image was dyed by a yellow dye, Solar Blue Yellow8 GO]. Acid Yellow 7 or Tartrazine C.I. Acid Yellow 23 and washed with abuffer solution having a pH of 5.0, a yellow image was obtained and theimage could be transferred onto a writing paper wetted by methanol orthe aforesaid gelatin layer-containing paper wetted by water.

Also, the same reaction was conducted at a pH of 11.5 using2,3-dioxynaphthalene (compound 17) instead of 1,2-diaminonaphthalene,for minutes,and

almost the same results were obtained.

EXAMPLE 4 The photographic light-sensitive film as in Example 2 wasexposed as in Example 2 and was processed in a solution having thefollowing composition and containing the reducing agent as shown inTable I:

Methacrylic acid 58.9 ml. Sodium carbonate (monohydrate) 43.0 g.Reducing agent shown in Table l. amt. shown in Table 1 Potassiummetabisulfite 3.0 g. Water 87.5 ml.

the amount necessary to adjust the pH to the value shown in Table 1.

After processing for the period of time shown in Table l at 30C., thefilm was fixed and washed with water as in Example 2 to provide an imageof polymethacrylic acid, which was dyed by a 1 percent solution of abasic dye, Rhodamine 6 GCP. The transmission densities to green lightwere measured about the exposed and the unexposed portions of thephotographic film before and after dyeing. The kind of reducing agent,the pH of the system at processing, the processing time, and the opticaldensities before and after dyeing are shown in Table l. 1

Amount of Processing Density of un- Density of reducing time exposedarea exposed area No. Reducing Agent agent (g) (min) before after beforeafter pH 1 a-Nziphthol 2.05 15 0.22 0.64 0.72 2.41 11.53 2l-Naphthol-Z-potassium sulfonate 1.18 20 0.10 1.07 0.1 1 2.88 11.55 3l-NuphthoI--1sodium sulfonute 1.07 50 0.09 1.16 0.09 1.41 1 1.55 4l-Nuphthol-S-sodium sulfonate 1.11 30 0.12 1.30 0.13 2.25 11.50 5B-Naphthol 6.48 30 0.08 0.71 0.0) 2.54 1 1.50 6 2-h \'drox\'-l-naphthouldehyde 7.74 50 0.14 0.54 0.16 1.90 l 1.50 72-.\uphtlioI-sodium sulfonate 1 1.07 50 0.07 0.35 0.09 0.48 1 1.60 82Sodium-6sotliuni sulfonzite 1 1.07 0.10 1.46 0.1-1- 1.68 1 1.50 92-.\';1phthol-7-sodium sillloimte l 1.07 40 0.25 1.12 0.20 1.78 1 1.3310 2Nuphthol-H-sodium siillonzite 1 1.07 -10 0.13 1.60 0.1-1 2.09 1 1.50l l Z-Hydroxy-l-nzlphthoic acid 8.46 40 0.17 1.00 0.18 2.23 11.50 12m-.\-(Lhydroxy-3-naphthoy1)phenvlenediaminc 5.00 70 0.22 3.10 0.32 3.621 1.50 13 [34 Z-h}Lilt)X)3-llklPlllhU)'i )ummoctlmnol 10.40 70 0.10 0.610.13 2.51 9.00 14 u-Nitrosrnlynuphthol 0.08 70 0.07 0.46 0.08 1.07 9.1015 Nuphthulornnge 1.00 70 0.10 0.37 0.12 1.64 11.55

Continued Amount of Processing Density of un Density of reducing timeexposed area exposed area No. Reducing Agent agent (g) (min) beforeafter before after pH 16 l-(1-hydroxy-2-nuphthyluzol-5-nitro-2- 0.50 300.40 1.37 0.44 2.73 11.45

nuplithol-4-sodium sulfonutu 17 2.3-Naphthulcncdiol 7.20 0.17 0.92 0.683.70 11.50 18 2.3-dihydroxynaphthalcne-o-sodium sulfonatc 1 1.79 40 0.080.28 0.06 1.32 I 1 1.50 19 l.5-t|ihydroxynaphthulcnc 7.20 20 0.08 0.550.28 1.63 9.00 20 1.7-d1hydroxynaphthulenc 0.16 30 0.08 0.35 0.14 1.849.15 21 l.7-dihydroXy-6-naphthoic acid 0.756 60 0.10 1.34 0.10 2.10 I9.05 22 a-nuphthylamine 0.44 50 0.08 0.42 0.05 0.57 9.05 23B-dicthyluminocthyl-a-nuphthylumine 8.32 70 0.12 0.52 0.12 0.66 10.50 i.24 thionalidc 3.52 70 0.15 0.69 0.16 1.77 10.50,

25 Z-nuphIhylaminc-8-sodium SL11fOllt1IC 10.04 70 0.09 0.43 0.07 1.12 11.50 i I 26 2-nuphthyluminc-4,8-tlisodium sulfonatc 15.61 70 0.10 0.410.15 0.91 11.50 27 1.2-nuphthulcnediaminc 0.71 10 0.09 0.25 0.48 2.939.00 28 l.5-naphthalencdiumine 7.1 1 0.11 0.30 0.16 1.90 1 1.50 292-umino-8-nuphthol-3.o-disulfonic acid 14.35 20 0.12 0.85 0.12 2.54 I11.50 30 l-umino-2-naphthol-4-sodium sult'onatc 0.01 40 0.12 0.51 0.221.41 9.03 31 1-amino-5-nuphthol 7.16 7 0.22 0.84 1.21 3.10 11.50 325-methzuicryloylamino1-nuphthol 10.22 25 0.18 0.25 0.26 1.80 11.50 338-oxyquinolin 6.53 70 0.08 0.22 0.08 0.56 1 1.50 344.8-di11ydroxyquinoIin-Z-curboxylic acid 6.00 30 0.09 0.29 0.12 2.2411.50, 35 4-hydroxyquinolin-2-curhoxylic acid 8.50 70 0.11 0.36 0.120.63 11.50 I 36 l-na hthol-Il-sulfonumidc sodium salt 1.00 30 0.18 2.510.19 3.34 11.50 37 2.4- ichlor-Lnuphthol 0.96 30 0.99 3.70 1.05 above 411.50 I 38 2.3diaminonaphthalcne 3.50 15 0.07 0.62 0.07 2.44 l 1.50

From the above results, it was confirmed that the density of the colorimage was higher in the exposed portions than in the unexposed portionsand hence the exposed portions were selectively dyed. This was alsoconfirmed by the fact that when the silver image of each sample wasremoved by a Farmers reducer, a clear red image was obtained.

When the reducing agent of compound 13 or 14 was used, the increase indensity was large and a clear red image was obtained without bleachingthe silver by a Farmers reducer. Also, the color image obtained abovecould be transferred onto a writing paper using methanol as in Example3.

EXAMPLE 5 By using the following films, A and B shown below, thepolymerization of a system of sodium methacrylate and 2,3-naphthalenediol (compound 17) was conducted.

Film A: After subbing both surfaces of a cellulose triacetate support,one of them was coated with an antihalation layer. The other surface wascoated with a gelatino middle grain size silver halide emulsioncontaining about 225 g. of gelatin, about 0.015 mole of iodine and about0.985 mole of bromine per one mole of silver, and having incorporatedtherein 0.5 g. of mucochloric acid per 100 g. of gelatin as a hardeningagent, a proper stabilizer, and a surface active agent so that the layercontained 60 mg. of silver per 100 cm.

Thereafter, a protective layer consisting of gelatin having a thicknessof about 1 micron was applied to the emulsion layer. The film thusprepared was of the type used for preparing positives by photogravure.

Film B: A film support having subbing layers and an antihalation layeras in Film A was coated with a gelatino fine grain silver halideemulsion containing about 204 g. of gelatin, about 0.012 mole of iodineand about 0.988 mole of iodine per one mole of silver, sensitized by arhodan complex of mono-valent gold, and having incorporated therein 0.3g. of 6-methyl-4-hydroxyl,3,3a,7-tetraazaindene per one mole of silveras a stabilizer, about 0.7 g. of mucochloric acid per 100 g. of gelatinas a hardening agent, and a proper surface active agent, so that thelayer contained 60 mg. of silver per 100 cm. Further, a protective layerof gelatin having a thickness of about 0.8 micron was applied to. the

emulsion layer. The photographiclight-sensitive film thus prepared wasof the type used for preparing line images or hard continuous tonepositives by photogra vure.

The two sample films were exposed as in Example 2 and processed in asolution having the following composition:

Sodium methacrylate 2,3-naphtha1ene diol (compound 17) 0. 2 g. Potassiummetabisulfite 3.0 Water 75 m 2N-sodium hydroxide amount necessary toadjust the pH to 1 1.5. 1

When the films were processed for 20 minutes at" 30C., faint brownimages were obtained. Each of the samples was fixed and washed as inExample 3 and divided into two parts, one of which was dyed using rho-'-damine 6 GCP as in Example 4. After drying, the densities of the dyedsample and the unprocessed sample I were measured as in Example 4, theresults of which 1 are shown in Table II.

In the exposed areas, a color image was formed although the formation ofthe silver image was scarcely observed, which showed that thepolymerization could 1 be initiated by the reduction of a very smallamount of silver.

solution of 1 percent sodium bicarbonate, and, afterallowing it to standfor 3 minutes, the transfer paper was separated from the sample toprovide a color image on the transfer paper.

Also, each sample thus dyed was wetted with water, I placed underpressure on the surface of a transfer paper as used in Example 3 andwetted by an aqueous luxes for 1 second through an optical step-wedgehaving a step difference of 0. l and processed in solutions in sample 4,and hence it was confirmed that the amount of the polymer formed bypolymerization corresponding to the same amount of exposure was largerin sample 4. Thus, it was confirmed that by the use of having thefollowing compositions, respectively. In this 5 a conventionaldeveloping agent together with the reexample, the effect of adding aconventional developducing agent of the present invention, thepolymerizaing agent is demonstrated. tion of the system was effectivelypromoted.

Sample No. l 2 3 4 5 6 Component Sodium methacrylate (g.) 100 I00 I00180 100 100 a-naphthol (g) 1.73 l.73 1.73 2,3-naphthalenediol (g.) 0.0.96 0.96 0.96 Catechol (mg) 0.17 1.7 p-methylaminophenol 0.01 0.1sulfate tmg.) Potassium metabisulfite(g) 4 4 4 4 4 4 Water tml.) 100 100100 100 100 100 2N-sodium hydroxide the amount necessary to adjust thepH of the system to l 1.5.

After processing for minutes at 30C., each sam- EXAMPLE 7 ple wasprocessed further as in Example 4. After being Five film Samples as inExample 6 were prepared and sufficiently fixed washed each Sample wasInto after exposure, were processed in a solution having the S i one f fi m if 5 following composition. In this example, the effect of ucer 0Comp ete y eac t e ermore using a quaternary salt with the reducingagent of this about samples and the Opncal denslty at the 5th inventionwas shown. As the quaternary salt, laurylstep was measured and aboutsamples 4, 5, and 6, the pyridinium chloride was used optical density ofthe 6th step was measured using a green filter, the results of which areshown in Table III.

S l N 1 3 4 Table III ampe O 2 5 Component Sample Density of Density ofNumber of final step No. unexposed area exposed area susceptible todyeing ziigz y g 100 I00 100 100 I 026 044 8 2,3-naphthalene 0.96 0.960.96 0.96 0.96 2 028 072 10 (g) 3 11 1% laurylpyridinium 2.5 9 22.5 4 10chloride (ml.)

meta isu ite( 6 044 159 11 40 Water (ml.) g 100 100 100. 100 1002N-Sodium hydroxide the amount necessary to adjust the pH of the systemto 11.5. The density shown above was that of the dye dyed to theselectively formed polymer in proportion to the amount of exposure andhence corresponds to the After Processing lomihutesa't30C-,the5amP1e$amount of polymer formed. Also, the number of final Were P further as inExample and the results steps susceptible to dyeing shown in the abovetable are shown In ab e was the step number through which the increaseof T ble V color density could be observed as compared with the a foggedportions when the sample thus dyed and Number of final bleached wasobserved by naked eye. That 1s, the num- Comm Density of Density forStep Susceptible ber corresponds to the minimum amount of exposure NO.exposed area 6th step to dyeing capable of selectively forming thepolymer; thus, the 1 l0 10 larger the number of the final step, thehigher the sensi- 8%? H tivity of the film. 3 0.46 1.97 12 Since thestep difference of the optical wedge used g 8 was 0.15, the fact thatsample 2 was 2 steps higher than sample 1 in the number of final stepsas shown in Table Shows that Sample 2 ga the Same extent of p y Theanalysis of the data can be done as in Example merllatlon as Sample 1wlth one-half of the exposure 6. Thus, the results showed that in thecase of using the amount for sample 1. In other words, the processing50- quaternary salt together with the reducing agent of this lLllIlOl'lused for PI'OCCSSlHg sample 2 gave the same efinvention almost the sameamount of polymer was bfect as the Case Where t Sample was exposed twiceas tained either when the exposure amount was less or much, as comparedwith processing the sample in the h h processing i d f time was less.processing solution used for processing sample 1. Also, EXA E 8 whensample 4 was compared with sample 6, the density corresponding to aso-called 'fog increased, but when the optical densities at the same 6thstage were compared, the increase in density by dyeing was larger Thefilm as in Example 2 was exposed to X -rays. Thereafter, the film wasprocessed in solution 17 of Example 4.

The X-ray exposure was conducted by using a cobalt X-ray tube made byPhilips Co. at 30 kv. and ma. The sample was exposed to the X-ray tubeat 1 cm. apart from the window of the X-ray tube while covering a partof the sample by a razor blade of 0.2 mm. in thickness.

The samples were each exposed for 1 second, 3 seconds or 10 seconds,respectively, and were processed for minutes at C. By this procedure,only the portions exposed to X-rays gave a silver image, and bysubjecting the image to the post-processing steps as in Example 7, theimage portions were dyed, which showed that polymethacrylic acid wasformed.

Thus, the process of this invention can be applied to a silver halideemulsion layer exposed to high energy rays, such as X-rays.

Further supplementing our discussion of the conventional developingagents and quaternary salts useful in the present invention, asdescribed at Pages 25 and 26 of this application, of particular interestis a developing agent having the formula:

i 2 IO w c wherein X represents a member selected from the groupconsisting of a halogen atom and a R SO R representing a member selectedfrom the group consisting of an aliphatic group and an aromatic group; Rrepresents a member selected from the group consisting of an alkyl grouphaving from 1 to 18 carbon atoms and a substituted alkyl group; Rrepresents a member selected from the group consisting of, an alkylgroup having from 1 to 5 carbon atoms, and a substituted alkyl group;and Z represents a member selected from the group consisting of a carbonatom and a nitrogen atom necessary to complete a S-membered or 6-membered heterocyclic ring.

Although the present invention has been adequately described in theforegoing specification and Examples included therein, it is readilyapparent that various modifications and changes can occur, withoutdeparting from the spirit and scope thereof.

What is claimed is:

1. A process for the formation of a polymer image which comprisesexposing a photographic silver halide emulsion so as to provide a latentimage and subse? quently, developing said latent image in the presenceof I one monomer of the group consisting of a vinylidene I wherein Rrepresents a hydrogen atom, a sulfone group, a substituted arylazo groupor a chlorine atom;

wherein R represents a hydrogen atom, a formyl group, a sulfone group,acarboxyl group, a nitroso group,-an arylazo group or an amino group; Rrepresents a hydrogen atom, -CONHR (R' represents an aryl group or analkyl group), or a hydroxyl group; R,

represents a hydrogen atom, a chlorine atom or a su1-; fone group; Rrepresents a hydrogen atom or anitro group; and R R and R eachrepresents a hydrogen 7 atom or a sulfone group;

iii. a-naphthylamine or a derivative thereof NHZ wherein R represents ahydrogen atom, a substituted I 7 alkyl group, an amino group, or ahydroxy group; R

wherein R represents a hydrogen atom or an amino group; R represents ahydrogen atom, a sulfone group or an amino group; R represents ahydrogen atom or a sulfone group; R represents a hydrogen atom or asulfone group, and R represents a hydrogen atom, a sulfone group or ahydroxyl group; and

v. oxyquinoline derivative wherein when R is a hydroxyl group, Rrepresents a hydrogen atom or a carboxyl group and R represents ahydrogen atom or a hyroxyl group; and when R; is a hydroxyl group, Rrepresents a carboxyl group and R represents a hydrogen atom; wherebysaid monomer is selectively polymerized at the areas having said latentimage in the presence of a sulfite ion and a developing agent, saidsulfite ion being present in at least 0.04 mol per liter.

2. The process of claim 1, wherein said polymerization reaction isconducted in the presence of a small amount of a quaternary salt havinga heteroaromatic ring including at least 1 nitrogen atom or having analiphatic amine, said quaternary salt having the following formulae(III) or (IV):

12 (III) (R N. R X (IV) wherein X" represents a member selected from thegroup consisting of a halogen atom and a R 80}, R representing a memberselected from the group consisting of an aliphatic group and an aromaticgroup; R represents a member selected from the group consisting of analkyl group having from I to 18 carbon atoms and a substituted alkylgroup; R represents a member selected from the group consisting of analkyl group having from 1 to carbon atoms, and a substituted alkylgroup; and Z represents a member selected from the group consisting of acarbon atom and a nitrogen atom necessary to complete a S-membered or 6-membered heterocyclic ring.

3. The process of claim 2, wherein the formed polymer image is dyed by adye.

34 4. A process for the formation of a polymer image as in claim 2,wherein said developing agent having the following general formula (I)or (II):

wherein R and R represent a member selected from the group consisting ofa hydroxyl group, an amino group and a NHR group, wherein R represents amember selected from the group consisting of an alkyl group having from1 to 5 carbon atoms and a substituted alkyl group.

5. The process of claim 4, wherein said quaternary salt is a quaternarysalt of pyridine.

6. The process of claim 5, wherein said quaternary salt is pyridiniumchloride.

7. The process of claim 1, wherein the formed polymer image is dyed by adye.

8. The process of claim 7 wherein dying is accomplished by the affinityof the dye for the formed polymer.

9. The process of claim 7, wherein the dye has a charge opposite to thecharge of said formed polymen.

10. A process for the formation of a polymer image as in claim 9 whereinsaid thus-formed polymer image is further dyed by a dye having a chargeopposite to the charge of said polymer when said polymer image iselectrolytically dissociated or combined with a hydrogen cation.

II.. The process of claim 10, wherein said polymer stems from a vinylcompound capable of providing a negative charge to said polymer, saidcompound being a member selected from the group consisting of a vinylcompound having a carboxyl group, a vinyl compound having a metal saltor an ammonium salt of a carboxylic acid, a vinyl compound having asulfonic acid group, and a vinyl compound having a metal salt or anammonium salt of sulfonic acid.

12. The process of claim 10, wherein said polymer stems from a vinylcompound capable of providing positive charges to said polymer, saidcompound being selected from the group consisting of a vinyl compoundhaving a basic nitrogen atom and a vinyl compound having a quaternarynitrogen salt.

13. The process of claim 12, wherein said vinyl compound may be joinedwith a water-soluble addition polymerizable vinyl compound having nocharge.

14. The process of claim 10, wherein said dye is an acid dye selectedfrom the group consisting of Acid Yellow No. 7, Acid Yellow No. 23, AcidRed No. 1, Acid Red No. 52, Acid Blue No. 9, Acid Blue No. 45, Acid BlueNo. 62, and Acid Violet No. 7.

15. The process of claim 10, wherein said dye is a basic dye selectedfrom the group consisting of Basic Yellow No. 1, Basic Yellow No. 2,Basic Red No. 1, Basic Red No. 2, Basic Blue No. 25, Basic Violet No. 3,and Basic Violet No. 10.

16. A process for the formation of a polymer image as in claim 1,wherein said compound is selected from the group consisting ofa-naphthol, l-naphthol-Z- potassium sulfonate, l-naphthol-4-sodiumsulfonate, l-naphthol-S-sodium sulfonate, B-naphthol,2-hydroxyl-naphthoaldehyde, Z-naphthol- 1 -sodium sulfonate,2-naphthol-6-sodium sulfonate, 2-naphthol-7-sodium sulfonate,2-naphthol-8-sodium sulfonate, 2-hydroxyl-naphthoic acid, m-N-(2-hyroxy-3- naphthoyl)phenylenediamine,B-(2-hydroxy-3-naphthoyl)aminoethanol, a-nitroso B-naphthol,naphtholorange, 1-(a-hydroxy-2-naphthylazo)-5-nitro-2- naphthol-4-sodiumsulfonate 2,3-naphthalenediol, 2,3- dihydroxynaphthalene-6-sodiumsulfonate, 1,5-dihydroxynaphthalene, l,7-dihydroxynaphthalene,l,7-dihydroxy-6-naphthoic acid, a-naphthylamine,B-diethylaminoethyl-a-naphthylamine, thionalide,2-naphthylamine-8-sodium sulfonate, 2-naphthylamine-4,8-disodiumsulfonate, l,2-naphthalenediamine, 1,5-naphthalenediamine,2-amino-8-naphthol-3,6- disulfonic acid, l-amin-2-naphthol-4-sodiumsulfonate, l-amino-S-naphthol naphthol, 8-oxyquinolin,4,8-dihydroxy-quinolin-2- carboxylic acid,4-hydroxyquinolin-Z-carboxylic acid, 1 -naphthol-3-sulfonamide sodium,2,4-dichloro-lnaphthol, and 2,3-diaminonaphthalene.

17. A process for the formation of a polymer image as in claim 1,wherein said monomer is selected from the group consisting ofacrylamide, acrylonitrile, N- hydroxymethyl acrylamide,N-tbutylacrylamide, methacrylic acid, acrylic acid, calcium acrylate,sodiumacrylate, methyl methacrylate, ethyl acrylate, vinyl pyrrolidone,dicyclopentadiene methacrylate vinyl butyrate, 2-vinylpyridine,4-vinylpyridine, vinylimidazole, potassium vinylbenzene sulfonate, vinylcarbazole, N,N'-methylene-bis-acrylamide, ethylene glycoldimethacrylate, diethylene glycol dimethacrylate, triet-hylene glycoldimethacrylate; polyethylene glycol dimethacrylate, divinylbenzene,bisphenol A dimethacrylate. butylene; dimethacrylate, trimethylolpropanetrimethacrylate, pentaerythrito tetraacrylate, and the like.

18. The process of claim 1, wherein said silver halide emulsion consistsofa dispersion system in which particles of silver halide are dispersedin a solution of high molecular weight polymer selected from the groupconsisting of gelatin, polyvinyl alcohol, polyvinyl pyrrolidone,polyacrylamide, carboxymethyl cellulose, oxyethyl ether, and dextrane,or mixtures of the aforementioned compounds.

19. The process of claim 1, wherein said sulfite ions stem from aprecursor which is a member selected from the group consisting ofalkaline metal sulfites, ammo- S-methaacryloylamino-l- 2-methyl-N-- niumsulfite, pyrosulfites, of alkaline metals, ammonium pyrosulfites, andaldehyde bisulfites.

20. The process of claim 19, wherein said aldehyde I bisulfite is amember selected from the group consisting formaldehyde bisulfite andglyoxal bisulfite.

21. The process of claim 1, wherein the amount. of i sulfite ionspresent is greater than 0.2 mol per liter of reaction system.

22. The process of claim 1, wherein said process is carried out at a pHgreater than 6.

23. The process of claim 1, wherein said process is carried out at a pHgreater than 7.

24. The process of claim 1, which further comprises the addition of aneffective amount of a thermal polymerization inhibitor to prevent thespontaneous overall thermal polymerization of the vinyl monomer.

25. The process of claim 24, wherein said inhibitor is a member selectedfrom the group consisting ,of pmethoxyphenol, hydroquinone, an alkylhydroquinone,-

and 2,6-di-t-butyl-p-cresol.

- 26. The process of claim 24, wherein said amount of polymerizationinhibitor ranges from l/l00,000 to 2/100 of the weight of the vinylmonomer.

27. The process of claim 1, wherein said vinyl monomer is present in anamount of from 1.30 to 30 times the weight of the high molecular weightcompound which is originally present in the emulsion.

28. The process of claim 27, wherein said vinyl monomer is present in anamount of from one-fourth to 4 times the weight of the high molecularweight compound originally present in the emulsion. I

29. The process of claim 1, wherein the silver halide is present in anamount of from 1.20 to 2 times the. amount of the high molecular weightcompound originally present in the system.

30. The process of claim 1, wherein said silver halide is present in anamount of from l/lO to one-half times the amount of the high molecularweight compound originally present in the system. 31. The process ofclaim 1, further comprising the 3 presence of a reducing agent in anamount of from one one-thousandths to 20 mols per mol of silver halide.

32. The process of claim 1, wherein said naphthol,

of from one one-hundredth to 1 mol per liter of pro- L I cessingsolution.

1. A PROCESS FOR THE FORMATION OF A POLYMER IMAGE WHICH COMPRISESEXPOSING A PHOTOGRAPHIC SILVER HALIDE EMULSION SO AS TO PROVIDE A LATENTIMAGE AND SUBSEQUENTLY, DEVELOPING SAID LATENT IMAGE IN THE PRESENCE OFONE MONOMER OF THE GROUP CONSISTING OF A VINYLIDENE MONOMER AND VINYLMONOMER, AND IN THE PRESENCE OF AT LEAST ONE REDUCING AGENT COMPOUNDSELECTED FROM THOSE REPRESENTED BY THE FOLLOWING FORMULAS: I. A-NAPHTHOLOR A DERIVATIVE THEREOF
 2. The process of claim 1, wherein saidpolymerization reaction is conducted in the presence of a small amountof a quaternary salt having a heteroaromatic ring including at least 1nitrogen atom or having an aliphatic amine, said quaternary salt havingthe following formulae (III) or (IV):
 3. The process of claim 2, whereinthe formed polymer iMage is dyed by a dye.
 4. A process for theformation of a polymer image as in claim 2, wherein said developingagent having the following general formula (I) or (II):
 5. The processof claim 4, wherein said quaternary salt is a quaternary salt ofpyridine.
 6. The process of claim 5, wherein said quaternary salt ispyridinium chloride.
 7. The process of claim 1, wherein the formedpolymer image is dyed by a dye.
 8. The process of claim 7 wherein dyingis accomplished by the affinity of the dye for the formed polymer. 9.The process of claim 7, wherein the dye has a charge opposite to thecharge of said formed polymer.
 10. A process for the formation of apolymer image as in claim 9 wherein said thus-formed polymer image isfurther dyed by a dye having a charge opposite to the charge of saidpolymer when said polymer image is electrolytically dissociated orcombined with a hydrogen cation. 11.. The process of claim 10, whereinsaid polymer stems from a vinyl compound capable of providing a negativecharge to said polymer, said compound being a member selected from thegroup consisting of a vinyl compound having a carboxyl group, a vinylcompound having a metal salt or an ammonium salt of a carboxylic acid, avinyl compound having a sulfonic acid group, and a vinyl compound havinga metal salt or an ammonium salt of sulfonic acid.
 12. The process ofclaim 10, wherein said polymer stems from a vinyl compound capable ofproviding positive charges to said polymer, said compound being selectedfrom the group consisting of a vinyl compound having a basic nitrogenatom and a vinyl compound having a quaternary nitrogen salt.
 13. Theprocess of claim 12, wherein said vinyl compound may be joined with awater-soluble addition polymerizable vinyl compound having no charge.14. The process of claim 10, wherein said dye is an acid dye selectedfrom the group consisting of Acid Yellow No. 7, Acid Yellow No. 23, AcidRed No. 1, Acid Red No. 52, Acid Blue No. 9, Acid Blue No. 45, Acid BlueNo. 62, and Acid Violet No.
 7. 15. The process of claim 10, wherein saiddye is a basic dye selected from the group consisting of Basic YellowNo. 1, Basic Yellow No. 2, Basic Red No. 1, Basic Red No. 2, Basic BlueNo. 25, Basic Violet No. 3, and Basic Violet No.
 10. 16. A process forthe formation of a polymer image as in claim 1, wherein said compound isselected from the group consisting of Alpha -naphthol,1-naphthol-2-potassium sulfonate, 1-naphthol-4-sodium sulfonate,1-naphthol-5-sodium sulfonate, Beta -naphthol,2-hydroxy-1-naphthoaldehyde, 2-naphthol-1-sodium sulfonate,2-naphthol-6-sodium sulfonate, 2-naphthol-7-sodium sulfonate,2-naphthol-8-sodium sulfonate, 2-hydroxy-1-naphthoic acid,m-N-(2-hyroxy-3-naphthoyl)phenylenediamine, Beta-(2-hydroxy-3-naphthoyl)aminoethanol, Alpha -nitroso Beta -naphthol,naphtholorange, 1-( Alpha-hydroxy-2-naphthylazo)-5-nitro-2-naphthol-4-sodium sulfonate2,3-naphthalenediol, 2,3-dihydroxynaphthalene-6-sodium sulfonate,1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,1,7-dihydroxy-6-naphthoic acid, Alpha -naphthylamine, Beta-diethylaminoethyl-Alpha -naphthylamine, thionalide,2-naphthylamine-8-sodium sulfonate, 2-naphthylamine-4,8-disodiumsulfonate, 1,2-naphthalenediamine, 1,5-nAphthalenediamine,2-amino-8-naphthol-3, 6-disulfonic acid, 1-amino-2-naphthol-4-sodiumsulfonate, 1-amino-5-naphthol 5-methaacryloylamino-1-naphthol,8-oxyquinolin, 4,8-dihydroxy-quinolin-2-carboxylic acid,4-hydroxyquinolin-2-carboxylic acid, 1-naphthol-3-sulfonamide sodium,2,4-dichloro-1-naphthol, and 2,3-diaminonaphthalene.
 17. A process forthe formation of a polymer image as in claim 1, wherein said monomer isselected from the group consisting of acrylamide, acrylonitrile,N-hydroxymethyl acrylamide, N-t-butylacrylamide, methacrylic acid,acrylic acid, calcium acrylate, sodium acrylate, methyl methacrylate,ethyl acrylate, vinyl pyrrolidone, dicyclopentadiene methacrylate vinylbutyrate, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-N-vinylimidazole,potassium vinylbenzene sulfonate, vinyl carbazole,N,N''-methylene-bis-acrylamide, ethylene glycol dimethacrylate,diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,polyethylene glycol dimethacrylate, divinylbenzene, bisphenol Adimethacrylate, butylene dimethacrylate, trimethylolpropanetrimethacrylate, pentaerythrito tetraacrylate, and the like.
 18. Theprocess of claim 1, wherein said silver halide emulsion consists of adispersion system in which particles of silver halide are dispersed in asolution of high molecular weight polymer selected from the groupconsisting of gelatin, polyvinyl alcohol, polyvinyl pyrrolidone,polyacrylamide, carboxymethyl cellulose, oxyethyl ether, and dextrane,or mixtures of the aforementioned compounds.
 19. The process of claim 1,wherein said sulfite ions stem from a precursor which is a memberselected from the group consisting of alkaline metal sulfites, ammoniumsulfite, pyrosulfites, of alkaline metals, ammonium pyrosulfites, andaldehyde bisulfites.
 20. The process of claim 19, wherein said aldehydebisulfite is a member selected from the group consisting formaldehydebisulfite and glyoxal bisulfite.
 21. The process of claim 1, wherein theamount of sulfite ions present is greater than 0.2 mol per liter ofreaction system.
 22. The process of claim 1, wherein said process iscarried out at a pH greater than
 6. 23. The process of claim 1, whereinsaid process is carried out at a pH greater than
 7. 24. The process ofclaim 1, which further comprises the addition of an effective amount ofa thermal polymerization inhibitor to prevent the spontaneous overallthermal polymerization of the vinyl monomer.
 25. The process of claim24, wherein said inhibitor is a member selected from the groupconsisting of p-methoxyphenol, hydroquinone, an alkyl hydroquinone, and2,6-di-t-butyl-p-cresol.
 26. The process of claim 24, wherein saidamount of polymerization inhibitor ranges from 1/100,000 to 2/100 of theweight of the vinyl monomer.
 27. The process of claim 1, wherein saidvinyl monomer is present in an amount of from 1.30 to 30 times theweight of the high molecular weight compound which is originally presentin the emulsion.
 28. The process of claim 27, wherein said vinyl monomeris present in an amount of from one-fourth to 4 times the weight of thehigh molecular weight compound originally present in the emulsion. 29.The process of claim 1, wherein the silver halide is present in anamount of from 1.20 to 2 times the amount of the high molecular weightcompound originally present in the system.
 30. The process of claim 1,wherein said silver halide is present in an amount of from 1/10 toone-half times the amount of the high molecular weight compoundoriginally present in the system.
 31. The process of claim 1, furthercomprising the presence of a reducing agent in an amount of from oneone-thousandths to 20 mols per mol of silver halide.
 32. The process ofclaim 1, wherein said naphthol, naphthylamine, or oxyquinoline ispresent in an amount of from one two-thousandths to 5 mols per liter ofprocessing solution.
 33. The process of claim 1, wherein said naphthol,naphthylamine or oxyquinoline is present in an amount of from oneone-hundredth to 1 mol per liter of processing solution.